JP2016013642A - Composition for three-dimensional molding, method for manufacturing three-dimensional molded article, and three-dimensional molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for three-dimensional molding, from which a three-dimensional molded article can be manufactured with high dimensional accuracy, and a three-dimensional molded article manufactured with high dimensional accuracy.SOLUTION: A method for manufacturing a three-dimensional molded article is provided, in which a three-dimensional molded article is manufactured by stacking layers 1. The method includes: a layer formation step of forming a layer 1 by using a composition for three-dimensional molding, which comprises particles, a binder resin, and an aqueous solvent; a drying step of heating the layer 1 to remove the aqueous solvent from the layer 1; and an ejection step of ejecting a binding solution 2 comprising a binder to the layer 1. The binder resin has an ammonium salt of a carboxylic acid as a functional group.

Description

  The present invention relates to a composition for three-dimensional modeling, a method for manufacturing a three-dimensional model, and a three-dimensional model.

  A technique for modeling a three-dimensional object while solidifying powder with a binding liquid is known (see, for example, Patent Document 1). In this technique, a three-dimensional object is formed by repeating the following operations. First, a molding slurry containing particles, an aqueous solvent, and a water-soluble polymer is thinly spread with a uniform thickness to form a layer, and a binder solution (binding solution) is discharged onto a desired portion of the layer to form a particle. Join bodies together. As a result, only the portion of the layer from which the binding liquid has been discharged is bonded to form a thin plate-like member (hereinafter referred to as “cross-sectional member”). Thereafter, the layer is further thinned on the layer, and the binding liquid is discharged to a desired portion. As a result, a new cross-sectional member is also formed at the portion of the newly formed layer where the binding liquid has been discharged. At this time, since the binding liquid discharged onto the powder layer soaks and reaches the previously formed cross-sectional member, the newly formed cross-sectional member is also bonded to the previously formed cross-sectional member. By repeating such operations and laminating thin plate-like cross-sectional members one by one, a three-dimensional object can be formed.

  With such 3D modeling technology, as long as there is 3D shape data of the object to be modeled, it is possible to immediately model by combining powder, and there is no need to create a mold prior to modeling. It is possible to form a three-dimensional object quickly and inexpensively. In addition, since thin plate-like cross-sectional members are layered one by one and shaped, for example, even a complex object having an internal structure can be formed as an integrated shaped object without being divided into a plurality of parts. .

  However, conventionally, when the modeling slurry is further supplied onto the formed layer (lower layer) and the layer (upper layer) is laminated, the lower layer particles are bound by the aqueous solvent contained in the modeling slurry. There was a problem that the water-soluble polymer that had been melted melted and the shape of the lower layer was deformed. For this reason, it was not possible to produce a three-dimensional structure with sufficient dimensional accuracy.

JP 2011-245712 A

  An object of the present invention is to provide a composition for three-dimensional modeling that can produce a three-dimensional structure with high dimensional accuracy, and a method for producing the three-dimensional structure, and three-dimensional manufactured with high dimensional accuracy. It is to provide a model.

Such an object is achieved by the present invention described below.
The composition for three-dimensional modeling of the present invention includes particles,
A binder resin,
An aqueous solvent,
The binder resin has a carboxylic acid ammonium salt as a functional group.

  Thereby, the composition for three-dimensional modeling which can manufacture a three-dimensional molded item with high dimensional accuracy can be provided.

The method for producing a three-dimensional structure of the present invention is a method for producing a three-dimensional structure by producing a three-dimensional structure by laminating layers,
A layer forming step of forming the layer using a three-dimensional modeling composition containing particles, a binder resin, and an aqueous solvent;
A drying step of removing the aqueous solvent from the layer by heating the layer;
A discharge step of discharging a binding liquid containing a binder to the layer;
The binder resin has a carboxylic acid ammonium salt as a functional group.

  Thereby, the manufacturing method of the three-dimensional structure which can manufacture a three-dimensional structure with high dimensional accuracy can be provided.

  In the three-dimensional structure manufacturing method of the present invention, in the drying step, it is preferable that the layer is heated so as to be equal to or higher than the glass transition temperature of the binder resin.

  Thereby, while removing an aqueous solvent and ammonia more reliably, particle | grains can be couple | bonded more firmly.

In the method for producing a three-dimensional structure according to the present invention, after repeatedly performing the layer forming step, the drying step, and the discharging step, a removal step of removing the particles that are not bound by the binder,
It is preferable that pH of the removal liquid used in the removal step is 9 or more.
Thereby, the particle | grains which are not couple | bonded with a binder can be removed more easily.

The three-dimensional structure of the present invention is manufactured by the method for manufacturing a three-dimensional structure of the present invention.
Thereby, the three-dimensional structure manufactured with high dimensional accuracy can be provided.

It is a schematic diagram which shows each process about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention. It is a schematic diagram which shows each process about suitable embodiment of the manufacturing method of the three-dimensional structure of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1. First, a method for manufacturing a three-dimensional structure according to the present invention will be described.

  FIG. 1 and FIG. 2 are schematic views showing each step in a preferred embodiment of the method for producing a three-dimensional structure of the present invention.

  As shown in FIG. 1 and FIG. 2, the manufacturing method of the present embodiment is a layer forming step for forming a layer 1 using a three-dimensional structure forming composition 1 ′ containing particles, a binder resin, and an aqueous solvent ( 1a, 1d), a drying step (1a, 1d) for heating and drying the layer 1, a discharge step (1b, 1e) for applying a binding liquid 2 containing a binder to the layer 1 by an inkjet method, and a layer A curing step (1c, 1f) for curing the binder contained in the binding liquid 2 applied to 1, and sequentially repeating these steps, and then, among the particles constituting each layer 1 And an unbound particle removing step (1h) for removing the unbound particles by the binder.

<Layer formation process>
First, a layer 1 is formed on a support (stage) 9 using a three-dimensional structure forming composition 1 ′ containing particles, a binder resin, and an aqueous solvent (1a).

  The support 9 has a flat surface (part to which the three-dimensional modeling composition 1 ′ is applied). Thereby, the layer 1 with high uniformity of thickness can be formed easily and reliably.

  The support 9 is preferably made of a high-strength material. Examples of the constituent material of the support 9 include various metal materials such as stainless steel.

  Further, the surface of the support 9 (part to which the three-dimensional modeling composition 1 ′ is applied) may be subjected to a surface treatment. Thereby, for example, the constituent material of the composition for three-dimensional modeling 1 ′ and the constituent material of the binding liquid 2 can be more effectively prevented from adhering to the support 9, or the durability of the support 9 can be particularly improved. It is possible to achieve excellent production of the three-dimensional structure 100 over a longer period of time. Examples of the material used for the surface treatment of the surface of the support 9 include fluorine resins such as polytetrafluoroethylene.

The three-dimensional modeling composition 1 ′ includes particles, a binder resin, and an aqueous solvent.
By including the binder resin, the particles can be bonded (temporarily fixed), and unwanted scattering of the particles can be effectively prevented. Thereby, the safety | security of an operator and the improvement of the dimensional accuracy of the three-dimensional structure 100 manufactured can be aimed at.

  In particular, the present invention is characterized in that the binder resin has a carboxylate ammonium salt as a functional group.

Usually, the binder resin (R- (COONH ₄ ) _m ) having a carboxylate ammonium salt as a functional group is dissociated and dissolved in an aqueous solvent as R- (COO ⁻ ) _m + mNH ₄ ⁺ . On the other hand, when the aqueous solvent and ammonia are removed by heating and drying in the drying step described in detail later, the binder resin becomes R- (COOH) _m , and the aqueous resin (neutral liquid) Difficult to dissolve.

  For this reason, in the case of forming the nth layer, when the three-dimensional modeling composition is applied on the n-1th layer, the n-1th layer is added by the aqueous solvent contained in the three-dimensional modeling composition. It is possible to prevent the binder resin that has bonded between the particles in the layer from being melted. As a result, a three-dimensional structure can be manufactured with high dimensional accuracy.

  This step can be performed, for example, by using a method such as a squeegee method, a screen printing method, a doctor blade method, or a spin coating method.

  The thickness of the layer 1 formed in this step is not particularly limited, but is preferably 10 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less. Thereby, while making the productivity of the three-dimensional structure 100 sufficiently excellent, the occurrence of unintentional irregularities in the manufactured three-dimensional structure 100 is more effectively prevented, and the three-dimensional structure 100 The dimensional accuracy can be made particularly excellent.

<Drying process>
In this step, the layer 1 formed using the three-dimensional modeling composition 1 ′ is dried by heating, and the aqueous solvent is removed from the layer 1. In this step, ammonia is removed from the binder resin along with the removal of the aqueous solvent.

  The heating temperature in the drying step is preferably equal to or higher than the glass transition temperature of the binder resin. Thereby, in a drying process, while being able to remove an aqueous solvent and ammonia more reliably, particle | grains can be temporarily fixed more reliably.

  Specifically, the heating temperature in the drying step is preferably 30 ° C. or higher and 140 ° C. or lower, and more preferably 40 ° C. or higher and 120 ° C. or lower. Thereby, an aqueous solvent and ammonia can be removed more reliably.

<Discharge process>
Thereafter, a binding liquid 2 containing a binder is discharged onto the layer 1 by an ink jet method (1b).

  In this step, the binding liquid 2 is selectively applied only to the portion of the layer 1 corresponding to the real part (the actual portion) of the three-dimensional structure 100.

In this step, since the binding liquid 2 is applied by an ink jet method, the binding liquid 2 can be applied with good reproducibility even if the application pattern of the binding liquid 2 has a fine shape. As a result, the dimensional accuracy of the finally obtained three-dimensional structure 100 can be made particularly high.
The binding liquid 2 will be described in detail later.

<Curing process>
Next, the binder applied to the layer 1 is cured to form the cured part 3 (1c). Thereby, the bond strength between particles can be made particularly excellent, and as a result, the mechanical strength and water resistance of the finally obtained three-dimensional structure 100 can be made particularly excellent.

  This step varies depending on the type of the curing component (binder). For example, when the curing component (binder) is thermosetting, it can be performed by heating, and when the curing component (binder) is photocurable. , Can be performed by irradiation with the corresponding light (for example, when the curing component is ultraviolet curable, it can be performed by irradiation with ultraviolet light).

  The discharge process and the curing process may be performed simultaneously. That is, before the entire pattern of one layer 1 is formed, the curing reaction may be sequentially advanced from the portion to which the binding liquid 2 is applied.

  Thereafter, the series of steps described above is repeated (see 1d, 1e, and 1f). Thereby, the particle | grains of the site | part to which the coupling | bonding liquid 2 was provided will be in the state couple | bonded among each said layer 1, and the three-dimensional structure 100 as a laminated body by which the layer 1 of such a state was laminated | stacked is obtained ( 1g).

  In addition, the binding liquid 2 applied to the layer 1 in the second and subsequent ejection steps (see 1d) is used for bonding particles constituting the layer 1, and part of the applied binding liquid 2 is , Contact and adhere to the lower layer 1. For this reason, the binding liquid 2 is used not only for bonding particles in each layer 1 but also for bonding particles between adjacent layers. As a result, the finally obtained three-dimensional structure 100 has excellent overall mechanical strength.

<Unbound particle removal step>
Then, after repeating the series of steps as described above, as a post-treatment step, among the particles constituting each layer 1, unbound particle removal step of removing particles not bound by the binder (unbound particles) (1h) is performed. Thereby, the three-dimensional structure 100 is taken out.

  As a specific method of this step, for example, a method of removing unbound particles with a brush, a method of removing unbound particles by suction, a method of blowing a gas such as air, a method of applying a liquid such as water ( Examples thereof include a method of immersing the laminate obtained as described above in a liquid, a method of spraying a liquid, and a method of applying vibration such as ultrasonic vibration. Moreover, it can carry out combining 2 or more types of methods selected from these.

In particular, the removal of unbound particles is preferably performed using a removal solution having a pH of 9 or more. Since the binder resin interposed between the unbound particles is R (—COOH) _m as described above, it is difficult to dissolve in a neutral liquid such as water. Therefore, by using a removal liquid having a pH of 9 or more, the binder resin can be dissolved and unbound particles can be easily removed.

2. Next, the three-dimensional modeling composition 1 ′ will be described in detail.

  The three-dimensional modeling composition 1 ′ includes a plurality of particles, a binder resin, and an aqueous solvent.

Hereinafter, each component will be described in detail.
<Particle>
The three-dimensional structure forming composition 1 ′ contains particles.

  Examples of the constituent material of the particles include inorganic materials, organic materials, and composites thereof.

  Examples of the inorganic material constituting the particles include various metals and metal compounds. Examples of the metal compound include various metal oxides such as silica, alumina, titanium oxide, zinc oxide, zircon oxide, tin oxide, magnesium oxide, and potassium titanate; various kinds such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide. Metal hydroxides; various metal nitrides such as silicon nitride, titanium nitride and aluminum nitride; various metal carbides such as silicon carbide and titanium carbide; various metal sulfides such as zinc sulfide; various metals such as calcium carbonate and magnesium carbonate Carbonates; sulfates of various metals such as calcium sulfate and magnesium sulfate; silicates of various metals such as calcium silicate and magnesium silicate; phosphates of various metals such as calcium phosphate; aluminum borate, magnesium borate, etc. And various metal borates and composites thereof.

  Moreover, as an organic material which comprises particle | grains, a synthetic resin, natural polymer, etc. are mentioned, for example, More specifically, polyethylene resin; Polypropylene; Polyethylene oxide; Polypropylene oxide, Polyethyleneimine; Polystyrene; Polyurethane; Polyurea; Polyester; Silicone resin; Acrylic silicone resin; Polymer having (meth) acrylic acid ester such as polymethyl methacrylate as a constituent monomer; Cross polymer having (meth) acrylic acid ester as a constituent monomer such as methyl methacrylate crosspolymer ( Polyethylene resin such as nylon 12, nylon 6, copolymer nylon, etc .; polyimide; carboxymethylcellulose; gelatin; starch; chitin; chitosan, polycarbonate, etc. It is below.

  Among the above, the particles are preferably composed of an inorganic material, more preferably composed of a metal oxide, and even more preferably composed of silica. Thereby, the characteristics such as mechanical strength and light resistance of the three-dimensional structure can be made particularly excellent. In addition, since silica is excellent in fluidity, it is advantageous for forming a layer having higher thickness uniformity, and the productivity and dimensional accuracy of the three-dimensional structure 100 are particularly excellent. Can do. Moreover, when the particles are made of silica, light scattering by the particles on the surface of the three-dimensional structure to be manufactured can be more effectively prevented.

  As silica, commercially available products can be suitably used. Specifically, FB-5D, FB-12D, FB3SDC, FB5SDC, FB7SDC (manufactured by Denki Kagaku Kogyo Co., Ltd.), Leoroseal QS-09, Leoroseal QS-10, Leoroseal QS-102, Leoroseal CP-102, LeoroSeal QS -20, Excelica SE-8, Excelica SE-15, Excelica UF-305, Excelica UF-310, Excelica UF-320, Excelica UF-345, Excelica UF-725 (above, manufactured by Tokuyama), Carplex FPS-1 , Carplex FPS-2, Carplex FPS-5, Carplex FPS-101, Carplex CS-5, Carplex # 80, Carplex # 67 (above, manufactured by DSL Japan), Nip seal ER, Nip seal RS- 150, d Pseal E-150J, nip seal E-1030, nip seal E-170, nip seal E-200A, nip seal E-75, nip seal E-743, nip seal E-74P, nip gel AZ-200, nip gel AZ-260, nip gel AZ-360 ( As mentioned above, Tosoh Silica Co., Ltd.) can be mentioned.

  The average particle diameter of the particles is not particularly limited, but is preferably 1 μm or more and 25 μm or less, and more preferably 1 μm or more and 10 μm or less. As a result, the mechanical strength of the three-dimensional structure 100 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 100 can be more effectively prevented. The dimensional accuracy of the molded article 100 can be made particularly excellent. In addition, the fluidity of the powder for three-dimensional modeling, the fluidity of the composition for three-dimensional modeling including the powder for three-dimensional modeling are particularly excellent, and the productivity of the three-dimensional modeling is particularly excellent. it can. In the present invention, the average particle diameter means a volume-based average particle diameter. For example, a dispersion obtained by adding a sample to methanol and dispersing for 3 minutes with an ultrasonic disperser (Coulter counter method particle size distribution analyzer ( It can be determined by measuring with a 50 μm aperture using COULTER ELECTRONICS INS TA-II type).

  The Dmax of the particles is preferably 3 μm or more and 40 μm or less, and more preferably 5 μm or more and 30 μm or less. As a result, the mechanical strength of the three-dimensional structure 100 can be made particularly excellent, and the occurrence of unintentional irregularities in the manufactured three-dimensional structure 100 can be more effectively prevented. The dimensional accuracy of the molded article 100 can be made particularly excellent. Moreover, the fluidity of the composition for three-dimensional modeling can be made particularly excellent, and the productivity of the three-dimensional modeling object 100 can be made particularly excellent. Moreover, the scattering of the light by particle | grains in the surface of the three-dimensional structure 100 manufactured can be prevented more effectively.

  The particles may have any shape, but preferably have a spherical shape. Thereby, the fluidity of the composition for three-dimensional modeling can be made particularly excellent, the productivity of the three-dimensional structure 100 can be made particularly excellent, and the unwillingness in the manufactured three-dimensional structure 100 can be achieved. Generation of unevenness and the like can be more effectively prevented, and the dimensional accuracy of the three-dimensional structure 100 can be made particularly excellent. Moreover, the scattering of the light by particle | grains in the surface of the three-dimensional structure 100 manufactured can be prevented more effectively.

  The content of the particles in the three-dimensional structure forming composition 1 ′ is preferably 5% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 70% by mass or less. Thereby, the mechanical strength of the finally obtained three-dimensional structure 100 can be made particularly excellent while the fluidity of the three-dimensional structure forming composition 1 ′ is sufficiently excellent.

≪Binder resin≫
The three-dimensional modeling composition 1 ′ includes a binder resin together with a plurality of particles. By including the binder resin, the particles can be bonded (temporarily fixed), and unwanted scattering of the particles can be effectively prevented. Thereby, the safety | security of an operator and the improvement of the dimensional accuracy of the three-dimensional structure 100 manufactured can be aimed at.

  In the present invention, the binder resin has a carboxylic acid ammonium salt as a functional group. Thereby, in the case of forming the nth layer, when the composition for 3D modeling 1 ′ is applied on the n−1th layer, the aqueous solvent contained in the composition for 3D modeling 1 ′ is used. It is possible to prevent the binder resin that has bonded between the particles of the (n-1) th layer from being melted. As a result, the three-dimensional structure 100 can be manufactured with high dimensional accuracy.

Examples of the binder resin include polyacrylic acid ammonium salt.
Specific examples of binder resin products include, for example, viscomate (above, Showa Denko), Aquaric NL (above, Nippon Shokubai), Aron A-210, A6114, AS-1100, AS-1800, A-30SL / A-7250 / CL-2 (manufactured by Toagosei Co., Ltd.) and the like.

  The content of the binder resin in the three-dimensional structure forming composition 1 'is preferably 20% by volume or less, more preferably 1% by volume or more and 5% by volume or less with respect to the volume of the particles. Thereby, the function of the binder resin as described above can be sufficiently exhibited, and the mechanical strength of the three-dimensional structure 100 can be made particularly excellent.

≪Aqueous solvent≫
The three-dimensional modeling composition 1 ′ may contain an aqueous solvent in addition to the binder resin and particles as described above. Thereby, the fluidity | liquidity of 3D modeling composition 1 'can be made especially excellent, and the productivity of the three-dimensional structure 100 can be made especially excellent.

  Examples of the aqueous solvent constituting the three-dimensional modeling composition 1 ′ include water; alcoholic solvents such as methanol, ethanol, and isopropanol; ketone solvents such as methyl ethyl ketone and acetone, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Glycol ether solvents such as propylene glycol 1-monomethyl ether 2-acetate, glycol ether acetate solvents such as propylene glycol 1-monoethyl ether 2-acetate; polyethylene glycol, polypropylene glycol, etc. One kind or a combination of two or more kinds can be used.

  Especially, it is preferable that the composition for 3D modeling 1 'contains water. Thereby, binder resin can be melt | dissolved more reliably, the fluidity | liquidity of 3D modeling composition 1 ', and the uniformity of the composition of the layer 1 formed using 3D modeling composition 1' are obtained. It can be made particularly excellent. In addition, water is easy to remove after the formation of the layer 1, and even when it remains in the three-dimensional structure 100, it is difficult to adversely affect water. Moreover, it is advantageous from the viewpoint of safety to the human body and environmental problems.

  The content of the aqueous solvent in the three-dimensional structure forming composition 1 'is preferably 5% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 80% by mass or less. As a result, the effects of including the aqueous solvent as described above are more remarkably exhibited, and the aqueous solvent can be easily removed in a short time during the manufacturing process of the three-dimensional structure 100. This is advantageous from the viewpoint of improving the productivity of the object 100.

  In particular, when the three-dimensional modeling composition 1 ′ contains water as a solvent, the content of water in the three-dimensional modeling composition 1 ′ is preferably 20% by mass or more and 85% by mass or less. It is more preferable that the content is not less than 80% by mass. Thereby, the effects as described above are more remarkably exhibited.

≪Other ingredients≫
In addition, the three-dimensional modeling composition 1 ′ may include components other than those described above. Examples of such components include a polymerization initiator; a polymerization accelerator; a penetration accelerator; a wetting agent (humectant); a fixing agent; an antifungal agent; an antiseptic; an antioxidant; an ultraviolet absorber; Examples include regulators.

3. Next, the binding liquid used for manufacturing the three-dimensional structure of the present invention will be described in detail.
The binding liquid 2 contains at least a binder and a light stabilizer b.

<< Binder >>
The binder is a component having a function of binding particles by curing.

  Such a binder is not particularly limited, but a binder having hydrophobicity (lipophilicity) is preferably used. Thereby, for example, when using particles that have been subjected to a hydrophobic treatment as particles, the affinity between the binding liquid and the particles can be made higher, and the binding liquid is applied to the layer 1, The binding liquid can suitably penetrate into the pores of the particles. As a result, the anchor effect by the binder is suitably exhibited, and the mechanical strength and water resistance of the finally obtained three-dimensional structure can be improved. In the present invention, the hydrophobic curable resin may be any resin having a sufficiently low affinity for water. For example, the solubility in water at 25 ° C. is 1 [g / 100 g water] or less. preferable.

  Examples of the binder include thermoplastic resins; thermosetting resins; various photo-curable resins such as visible light curable resins, ultraviolet curable resins, and infrared curable resins that are cured by light in the visible light region; Resin etc. are mentioned, It can use combining 1 type (s) or 2 or more types selected from these. Among these, from the viewpoint of the mechanical strength of the obtained three-dimensional structure, the productivity of the three-dimensional structure, and the like, the binder is preferably a curable resin. Among various curable resins, in particular, from the viewpoint of mechanical strength of the obtained three-dimensional structure, productivity of the three-dimensional structure, storage stability of the binding liquid, etc., in particular, an ultraviolet curable resin (polymerizable compound). Is preferred.

  As the ultraviolet curable resin (polymerizable compound), a resin in which addition polymerization or ring-opening polymerization is initiated by irradiation with ultraviolet rays by radical species or cationic species generated from a photopolymerization initiator, and a polymer is preferably used. . Examples of the polymerization mode of addition polymerization include radical, cation, anion, metathesis, and coordination polymerization. Examples of the ring-opening polymerization method include cation, anion, radical, metathesis, and coordination polymerization.

  Examples of the addition polymerizable compound include compounds having at least one ethylenically unsaturated double bond. As the addition polymerizable compound, a compound having at least one, preferably two or more terminal ethylenically unsaturated bonds can be preferably used.

  The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound and a polyfunctional polymerizable compound, or a mixture thereof. Examples of the monofunctional polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like. As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

  In addition, unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl group, amino group, mercapto group and the like, addition products of isocyanates and epoxies, dehydration condensation products of carboxylic acids, etc. Can be used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with alcohols, amines and thiols, as well as removal of halogen groups, tosyloxy groups, etc. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasing substituent and an alcohol, amine or thiol can also be used.

  Specific examples of the radical polymerizable compound that is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound include, for example, (meth) acrylic acid ester, which is either monofunctional or polyfunctional. Can also be used.

  Specific examples of the monofunctional (meth) acrylate include, for example, tolyloxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isobornyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. are mentioned.

  Specific examples of the bifunctional (meth) acrylate include, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, penta Erythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, dipropylene glycol diacrylate, tripropylene Recall diacrylate and the like.

  Specific examples of the trifunctional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((Meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri ( Data) acrylate, and the like.

  Specific examples of the tetrafunctional (meth) acrylate include, for example, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate.

  Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Specific examples of the hexafunctional (meth) acrylate include, for example, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa ( And (meth) acrylate.

  Examples of the polymerizable compound other than (meth) acrylate include itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester and the like.

  Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diesterate. Examples include itaconate and sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

  Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5240, Japanese Patent Application Laid-Open No. 59-5241, Japanese Patent Application Laid-Open No. 2-226149, and those containing an amino group described in Japanese Patent Application Laid-Open No. 1-165613 are also used. be able to.

  Specific examples of the amide monomer of unsaturated carboxylic acid and aliphatic polyvalent amine compound include, for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexa. Examples include methylene bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, a urethane-based addition polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. As such a specific example, for example, one molecule described in JP-B-48-41708 A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (1) to a polyisocyanate compound having two or more isocyanate groups. Etc.

^{_{CH 2 = C (R 1)}} COOCH 2 CH (R 2) OH (1)
(However, in formula (1), R ¹ and R ² each independently represent H or CH ^3. )

  In the present invention, a cationic ring-opening polymerizable compound having at least one cyclic ether group such as an epoxy group or an oxetane group in the molecule can be suitably used as the ultraviolet curable resin (polymerizable compound).

  Examples of the cationic polymerizable compound include a curable compound containing a ring-opening polymerizable group, and among them, a heterocyclic group-containing curable compound is particularly preferable. Such curable compounds include, for example, epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic imino ethers such as oxazoline derivatives, vinyl ethers, etc. Among them, epoxy derivatives, oxetanes, etc. Derivatives and vinyl ethers are preferred.

  Examples of preferred epoxy derivatives include monofunctional glycidyl ethers, polyfunctional glycidyl ethers, monofunctional alicyclic epoxies, polyfunctional alicyclic epoxies, and the like.

  Specific examples of glycidyl ethers include, for example, diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, etc.), trifunctional or higher glycidyl ethers (for example, trimethylolethane triglycidyl). Ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), tetra- or higher functional glycidyl ethers (for example, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, poly of cresol novolac resin) Glycidyl ether, polyglycidyl ether of phenol novolac resin, etc.), alicyclic epoxies (eg, Celoxide 2) 21P, Celoxide 2081, Epolide GT-301, Epolide GT-401, EHPE (manufactured by Daicel Chemical Industries, Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc., oxetanes (eg, OX-SQ, PNOX-1009) (Above, manufactured by Toa Gosei Co., Ltd.)) and the like.

  As the polymerizable compound, an alicyclic epoxy derivative can be preferably used. The “alicyclic epoxy group” refers to a partial structure obtained by epoxidizing a double bond of a cycloalkene ring such as a cyclopentene group or a cyclohexene group with an appropriate oxidizing agent such as hydrogen peroxide or peracid.

  The alicyclic epoxy compound is preferably a polyfunctional alicyclic epoxy having two or more cyclohexene oxide groups or cyclopentene oxide groups in one molecule. Specific examples of the alicyclic epoxy compound include, for example, 4-vinylcyclohexylene dioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, Examples include di (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, di (2,3-epoxy-6-methylcyclohexylmethyl) adipate, and dicyclopentadiene dioxide.

  The glycidyl compound which has a normal epoxy group which does not have an alicyclic structure in a molecule | numerator can be used independently, or can also be used together with the said alicyclic epoxy compound.

  Examples of such normal glycidyl compounds include glycidyl ether compounds and glycidyl ester compounds, but it is preferable to use glycidyl ether compounds in combination.

  Specific examples of the glycidyl ether compound include 1,3-bis (2,3-epoxypropyloxy) benzene, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac. Glycidyl ether compounds such as epoxy resin, trisphenol methane epoxy resin, aliphatic glycidyl ethers such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane tritriglycidyl ether Compounds and the like. Examples of the glycidyl ester include a glycidyl ester of linolenic acid dimer.

  As the polymerizable compound, a compound having an oxetanyl group which is a 4-membered cyclic ether (hereinafter, also simply referred to as “oxetane compound”) can be used. An oxetanyl group-containing compound is a compound having one or more oxetanyl groups in one molecule.

  The content of the binder in the binding liquid is preferably 80% by mass or more, and more preferably 85% by mass or more. Thereby, the mechanical strength of the finally obtained three-dimensional structure can be made particularly excellent.

≪Other ingredients≫
Moreover, the binding liquid 2 may contain components other than those described above. Examples of such components include various colorants such as pigments and dyes; dispersants; surfactants; polymerization initiators; polymerization accelerators; solvents; penetration enhancers; wetting agents (humectants); Examples include glazes; antiseptics; antioxidants; ultraviolet absorbers; chelating agents; pH adjusters; thickeners; fillers;

  In particular, when the binding liquid 2 contains a colorant, the three-dimensional structure 100 colored in a color corresponding to the color of the colorant can be obtained.

  In particular, the light resistance of the binding liquid 2 and the three-dimensional structure 100 can be improved by including a pigment as the colorant. As the pigment, either an inorganic pigment or an organic pigment can be used.

Examples of the inorganic pigment include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, titanium oxide, and the like, and one kind selected from these. Alternatively, two or more kinds can be used in combination.
Among the inorganic pigments, titanium oxide is preferable in order to exhibit a preferable white color.

  Examples of the organic pigment include insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments and the like can be mentioned, and one or more selected from these can be used in combination.

  More specifically, as carbon black used as a black (black) pigment, for example, No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B and the like (manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (and above, manufactured by Columbia Columbia), Regal 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (above, manufactured by CABOT JAPAN K. C. Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6S Degussa)).

  Examples of white pigments include C.I. I. Pigment white 6, 18, 21 and the like.

  Examples of yellow (yellow) pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 150, 151, 153, 154, 155, 167, 172, 180 and the like.

  Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of the violet (cyan) pigment include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4, 60 and the like.

  Examples of other pigments include C.I. I. Pigment green 7,10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, and the like.

  When the binding liquid 2 contains a pigment, the average particle size of the pigment is preferably 300 nm or less, and more preferably 50 nm or more and 250 nm or less. Thereby, the discharge stability of the binding liquid 2 and the dispersion stability of the pigment in the binding liquid 2 can be made particularly excellent, and an image with better image quality can be formed.

  Specific examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive black 3, 4, 35 etc. are mentioned.

  When the binding liquid 2 contains a colorant, the content of the colorant in the binding liquid 2 is preferably 1% by mass or more and 20% by mass or less. Thereby, particularly excellent concealability and color reproducibility can be obtained.

  In particular, when the binding liquid 2 contains titanium oxide as a colorant, the content of titanium oxide in the binding liquid 2 is preferably 12% by mass or more and 24% by mass or less, and more preferably 14% by mass or more and 20% by mass. The following is more preferable. Thereby, the especially outstanding concealment property and sedimentation recovery property are obtained.

  When the binding liquid 2 contains a pigment, the dispersibility of the pigment can be further improved if it further contains a dispersant. As a result, a partial decrease in mechanical strength due to pigment bias can be more effectively suppressed.

  Although it does not specifically limit as a dispersing agent, For example, the dispersing agent currently used in preparing pigment dispersion liquids, such as a polymer dispersing agent, is mentioned. Specific examples of the polymer dispersant include, for example, polyoxyalkylene polyalkylene polyamine, vinyl polymer and copolymer, acrylic polymer and copolymer, polyester, polyamide, polyimide, polyurethane, amino polymer, silicon-containing polymer, and sulfur-containing polymer. , Fluorine-containing polymers, and epoxy resins having one or more types as main components. Commercially available polymer dispersants include, for example, Ajinomoto Fine Techno Co., Ltd. Ajisper series, Solsperse series (Solsperse 36000, etc.) available from Noveon, BYK Co., Ltd. Dispersic series, Enomoto Kasei The company's Disparon series, etc. are listed.

  When the binding liquid 2 contains a surfactant, the permeability to the layer and the abrasion resistance of the three-dimensional structure 100 can be further improved. The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone as a silicone-based surfactant can be used, and among them, polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Is preferably used. Specific examples of the surfactant include, for example, BYK-347, BYK-348, BYK-UV3500, 3510, 3530, 3570 (above, trade names manufactured by BYK).

  The binding liquid 2 may include a solvent. Thereby, the viscosity of the binding liquid 2 can be suitably adjusted, and even when the binding liquid 2 contains a high-viscosity component, the ejection stability of the binding liquid 2 by the ink jet method is particularly excellent. Can do.

  Examples of the solvent include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ethyl acetate, n-propyl acetate, iso-acetate Acetates such as propyl, n-butyl acetate and iso-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl n-butyl ketone, diisopropyl ketone, acetylacetone, etc. Ketones: Examples include alcohols such as ethanol, propanol, and butanol, and one or more selected from these can be used in combination.

  Further, the viscosity of the binding liquid 2 is preferably 10 mPa · s or more and 25 mPa · s or less, and more preferably 15 mPa · s or more and 20 mPa · s or less. Thereby, the discharge stability of the binding liquid 2 by the ink jet method can be made particularly excellent. In addition, in this specification, a viscosity means the value measured in 25 degreeC using an E-type viscosity meter (Tokyo Keiki Co., Ltd. VISCONIC ELD).

Moreover, you may use multiple types of binding liquid 2 for manufacture of the three-dimensional structure 100. FIG.
For example, a binding liquid 2 containing a colorant (color ink) and a binding liquid 2 containing no colorant (clear ink) may be used. Accordingly, for example, the binding liquid 2 containing a colorant is used as the binding liquid 2 to be applied to the area that affects the color tone on the appearance of the three-dimensional structure 100, and the color tone is affected on the appearance of the three-dimensional structure 100. You may use the coupling | bonding liquid 2 which does not contain a coloring agent as the coupling | bonding liquid 2 provided to the area | region which does not give. Further, in the finally obtained three-dimensional structure 100, an area (coat layer) is formed on the outer surface of the area formed using the binding liquid 2 containing the colorant using the binding liquid 2 containing no colorant. You may use together multiple types of binding liquid 2 so that it may provide.

  For example, you may use the multiple types of binding liquid 2 containing the coloring agent of a different composition. Thereby, the color reproduction range which can be expressed can be made wide by the combination of these binding liquids 2.

  When a plurality of types of binding liquids 2 are used, it is preferable to use at least a blue-purple (cyan) binding liquid 2, a reddish-purple (magenta) binding liquid 2, and a yellow (yellow) binding liquid 2. Thereby, the color reproduction area which can be expressed by the combination of these binding liquids 2 can be made wider.

  Moreover, the following effects can be obtained by using the white binding liquid 2 in combination with another colored binding liquid 2, for example. That is, the finally obtained three-dimensional structure 100 is overlapped with the first region to which the white (white) binding liquid 2 is applied and the first region, and is on the outer surface side of the first region. And a region to which a colored binding liquid 2 other than white is applied. Thereby, the 1st area | region to which the white (white) coupling | bonding liquid 2 was provided can exhibit concealment property, and can improve the saturation of the three-dimensional structure 100 more.

4). Three-dimensional structure The three-dimensional structure of the present invention is manufactured using the method for manufacturing a three-dimensional structure as described above. Thereby, the three-dimensional structure excellent in dimensional accuracy can be provided.

  The use of the three-dimensional structure of the present invention is not particularly limited, and examples thereof include appreciation objects / exhibits such as dolls and figures; medical devices such as implants.

  Moreover, the three-dimensional structure of the present invention may be applied to any of prototypes, mass-produced products, and custom-made products.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  More specifically, for example, in the above-described embodiment, in addition to the layer formation step, the drying step, and the discharge step, the curing step has been described as being repeatedly performed together with the layer formation step, the drying step, and the discharge step. The curing step may not be repeated. For example, it may be performed collectively after forming a laminate including a plurality of uncured layers.

  Moreover, in the manufacturing method of this invention, you may perform a pre-processing process and a post-processing process as needed.

As a pre-processing process, the cleaning process of a support body (stage) etc. are mentioned, for example.
As the post-treatment process, for example, a cleaning process, a shape adjustment process for deburring, a coloring process, a coating layer forming process, a light irradiation process or a heat treatment for surely curing an uncured ultraviolet curable resin is performed. Examples include an ultraviolet curable resin curing completion step.

  Moreover, although embodiment mentioned above demonstrated as what provides a binding liquid with respect to all the layers, you may have the layer to which a binding liquid is not provided. For example, the bonding liquid may not be applied to the layer formed immediately above the support (stage), and the layer may function as a sacrificial layer.

  In the above-described embodiment, the case where the ejection step is performed by the ink jet method has been mainly described, but the ejection step may be performed using another method (for example, another printing method).

DESCRIPTION OF SYMBOLS 1 '... Composition for three-dimensional modeling 1 ... Layer 2 ... Binding liquid 3 ... Curing part 100 ... Three-dimensional modeling thing 9 ... Support body (stage)

Claims (5)

Particles,
A binder resin,
An aqueous solvent,
The composition for three-dimensional modeling, wherein the binder resin has a carboxylate ammonium salt as a functional group. It is a manufacturing method of a three-dimensional structure that manufactures a three-dimensional structure by laminating layers,
A layer forming step of forming the layer using a three-dimensional modeling composition containing particles, a binder resin, and an aqueous solvent;
A drying step of removing the aqueous solvent from the layer by heating the layer;
A discharge step of discharging a binding liquid containing a binder to the layer;
The method for producing a three-dimensional structure, wherein the binder resin has an ammonium carboxylate as a functional group.   The method for producing a three-dimensional structure according to claim 2, wherein in the drying step, the layer is heated so as to be equal to or higher than a glass transition temperature of the binder resin. After repeatedly performing the layer forming step, the drying step, and the discharging step, a removal step of removing the particles that are not bound by the binder,
The method for producing a three-dimensional structure according to any one of claims 2 to 3, wherein the pH of the removal liquid used in the removal step is 9 or more.   A three-dimensional structure manufactured by the method for manufacturing a three-dimensional structure according to any one of claims 2 to 4.

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